Winterized glyceride oil and process of producing the same



fiatenteci Sept. 16, 1952 WINTERIZED GLYCERIDE 011. AND PROCESS OFPRODUCING THE SAME Karl F. Mattil, Chicago, 111., assignor to Swift &

Company, Chicago, 111., a corporation of Illinois No Drawing.Application July 24, 1950, Serial No. 175,659

11 Claims.

This invention relates to treating fatty glyceride material, and it hasto do more particularly with the manufacture of an improved glyceride o1In the processing of glyceride fatty material an important problem isthe removal of the high melting point glycerides which are normallysolid at room temperatures and Which tend to separate from the oil atrelatively high temperatures. The conditioning of a glyceride fattymaterial to effectuate separation of the liquid fats from theundesirable solid fats must be carefully controlled in order to obtainthe solid fat in a crystalline form suitable for filtration. Under thebest conditions, filtration is inefficient, for the solid fats oftenseparate as extremely small particles and remain suspended in the oil ascolloidal dispersions, thus making the straining operation verydifficult.

I have now discovered that certain compositions hereinafter to bedescribed and referred to as crystal inhibiting and modifying agents areextremely useful in prolonging the cold test of glyceride oils and infacilitating the Winterizing process.

In winterizing" a glyceride oil or processing a fatty material such assperm oil or white grease to obtain lard oil, the conditioning of theoil or fatty material to effectuate separation of the liquid fats fromthe solid fats must be carefully controlled in order to obtain the solidfat in a crystalline form suitable for filtration. Under the bestpresent-day conditions filtration is ineflicient, for the solid fatsoften separate as extremely small particles and remain suspended in theoil as colloidal dispersions, thus making the straining operation verydiflicult. The difficulties attending the process of Winterizing ashitherto practiced may be overcome by incorporating into the glycerideoil or glyceride fatty material, such as sperm oil or white grease, asmall amount of the crystal inhibitors and modifiers, hereinafterdescribed. I have found that the addition of such substance profoundlyaffects crystallization whereby the crystals of the solid fats arerendered firmer and better defined. The form f the crystals is soimproved that a more facile and complete separation of the undesirablesolids from the liquid constituents of the oil is effected. In additionto improving winterization, these substances are usually present insufiicient amounts to lengthen substantially the cold test of the oil,although this effect is not so pronounced as that which results when thecrystal inhibitor is added after the oil has been winterized.

An important object of the present invention is,

therefore, to provide an improved method for separating the solidifiedfat crystals from the liquid fats in glyceride fatty material.

Another object of the present invention is to provide a method ofimproving the Winterizing of glyceride oils.

Still another object of the invention is to provide a glyceride oilhaving an improved cold test.

A still further object of the present invention is to provide animproved glyceride oil which will remain clear and homogeneous for longperiods of time at relatively low temperatures. v

Another object of the invention is to provide an improved glyceride oilwhich will exhibit good stability at relatively low temperatures whenincorporated in an emulsion.

Additional objects of the invention will be apparent from thedescription and claims to follow.

Broadly, the invention contemplates the addition to a glyceride oil orglyceride fatty material, either before or after winterization, of asmall amount of an oil-soluble polymerization product of esters havingvinyl or substituted vinyl group, according to the following generalformula; namely, esters of the formula wherein X is a hydrogen atom andalkyl or aromatic hydrocarbon group, and Y is o Jae-R in which R is amonovalent hydrocarbon radical containing more than 4 carbon atoms or anether derivative of said hydrocarbon radical.

' Compounds of the above type are the esters of acrylic acid or of itsalpha-alkyl or alpha-aryl substitution products and monohydric alcoholscontaining more than 4 carbon atoms, such as octyl, decyl, lauryl, orcetyl esters of acrylic acid, alpha-methacrylic acid, and otheralpha-substituted homogenous or acrylic acid, as more fully described inU. S. Patent 2,091,627.

The most effective polymers for the present purpose are the oil-solublepolymerized esters of acrylic acid or alpha-methacrylic acid andmonohydric, saturated, primary aliphatic alcohols containing from 12 to18 carbon atoms or molecules, such as lauryl, cetyl, or octadecylesters.

These esters need not be pure but may be mixtures of one or more of thehigher aliphatic alcohols and the acrylic or methacrylic acidpolymerization products. A mixture of two or more of the foregoingpolymers may also be used.

These polymers are preferably prepared by heating the monomeric estersor mixtures thereof at 70-100 C. in the presence of small amounts ofpolymerization-inducing catalysts, such as peroxides or ozonides, asmore fully disclosed in U. S. Patents 2,100,993 and 2,114,233.

Preferably the amount of the foregoing crystal modifiers used rangesfrom .005 to 1.0 per cent. Where it is desired to add the crystalmodifier prior to the Winterizing operation to facilitate filtration, itis often advantageous to add additional amounts to replace that whichmay be removed with the solid matter during filtration. Larger amountsof the crystallization inhibitor may be used but generally is notcommercially advisable.

The following examples illustrate how the invention may be practiced,and are not intended to limit the scope of the invention:

Example I To 100 grains of winterized cottonseed salad oil having a coldtest of about 9 hours was added 1.0 per cent of the oil-solublepolymerization product of an ester of alpha-methacrylic acid and laurylalcohol. After the said polymerization product is uniformly distributedthroughout the oil, a cold test of the treated oil gave a value of 45hours.

Example [I To 100 grams of winterized cottonseed salad oil having a coldtest of about 9 hours was added 0.10 per cent of the oil-solublepolymerization product of an ester of alpha-methacrylic acid and laurylalcohol. The cold test of the treated salad oil gave a value of 35hours.

Example III To a sample of winterized cottonseed oil having a cold testof 15 hours, 0.02 per cent of cetylalpha-methacrylate soluble in oil wasadded and uniformly distributed therethrough. The oil containing theabove crystal-inhibiting agent exhibited a cold test of 60 hours.

Example I V Mayonnaise made with a winterized cottonseed salad oilcontaining 0.02 per cent n-oetyl-acrylate soluble in oil was placed in acooler maintained at a temperature of 28 F., and the mayonnaise emulsiondid not break until after being held seven days at the said temperature.A similar sample of mayonnaise stood up for two days when placed in acooler maintained at a temperature of 24 F. The control sample ofmayonnaise consisting of a winterized cottonseed oil having the sameinitial cold test but which was not treated with a crystal-inhibitingagent broke in less than one day at 24 F. and less than three days at 28F.

Example V A sample of refined and bleached cottonseed oil containing0.20 per cent lauryl-alpha-methacrylate soluble in oil was placed in acooler maintained at 45 F. for three days. Upon filtering the sample bygravity through a standard filter cloth, the yield of oil from thesample containing the above crystal-inhibiting agent was 82 per cent.The yield of the control sample of the refined and bleached cottonseedoil was '71 per cent.

Example VI To a sample of white grease was added 0.10 per cent of anester of alpha-methacrylic acid and octadecyl alcohol soluble in oil andthe sample seeded for five days at F. The yield of oil upon pressing thewhite grease treated in the foregoing manner was per cent. The yieldfrom the control chamber of the white grease containing nocrystal-inhibiting agent was 55 per cent.

Example VII A sample of crude sperm oil containing 0.05 per centn-lauryl acrylate soluble in oil was seeded in 45 F. for six days andthen pressed. The yield of winterized sperm oil treated in the foregoingmanner was 82 per cent. The yield of the control sample of the sperm oilwas per cent.

As hereinbefore mentioned, the above-described crystal inhibitors andmodifiers may be added to the glyceride materials before or afterwinterization. The addition of the crystal modifier before winterizationserves primarily to facilitate and improve the Winterizing operation.Although crystal formation is retarded in the presence of the additive,once the crystals are formed they are of such form as to settle quickly,and because of the nature of the crystals a sharp separation of theundesired solids from the liquid constituents of the oil is possible. Anadvantage of the improved filtering operation is that the yields of oilsare greatly increased over the Winterizing process as hithertopracticed. Often it is desirable to add an additional small amount ofthe additive after the winterization operation so as to replace thatwhich was filtered out along with the high melting glyceride crystals.

In case it is desired to have a glyceride oil of very long cold test,the materials described above are added to the oil after it has beenwinterized, the extent of lengthening the cold test depending on thequality of oil chosen, the additive being more efiective'in an oilhaving an original 'longer cold test than in an oil of shorter coldtest.

Another important advantage of the invention flows from the use of oiltreated with the described agents in emulsions. An emulsion, such asmayonnaise, containing a vegetable oil treated in the foregoing mannerwill remain stable for muchlonger periods of time than has been hithertopossible to maintain such emulsions.

While the invention described herein has particular application to themanufacture of salad oils, the invention is not limited to such anoperation. It should be understood that the invention is useful intreating various fatty glyceride materials wherein a solid orcrystalline fraction is separated from a liquid fraction as in theseparation of a crystalline fraction from animal oils such as lard oil,oleo oil, sperm oil, and animal fats and greases used in the preparationof lard oil and the like. In treating various vegetable and animal oilsit is often desirable to separate a solid fraction such as stearin,palmitin, spermaceti and other high melting point fractions bycrystallizing such fraction with or without the presence of a solventand then separating the crystallized fraction by cold settling,pressing, centrifuging of filtration. The crystal modifying agentsherein described may also be used to modify the crystal structure of thesolid phase whereby it may be more readily separated from the liquidphase when extracted with a suitable solvent.

Obviously many modifications and variations of the inventionhereinbefore set forth may be made without departing from the spirit andscope thereof, and therefore only such limitations should be imposed asare indicated in the appended claims.

I c aim:

l. A glyceride oil composition of improved cold .test, comprising aglyceride oil having incorporated therein a small amount of anoil-soluble product to improve the cold test thereof, said product beingthe polymerization product of esters containing a radical selected fromthe group consisting of vinyl and substituted vinyl compounds accordingto the general formula wherein X is selected from the group consistingof hydrogen and alkyl and aromatic hydrocarbon radicals and Y isselected from the group having the formula and -(||JOR wherein R isselected from the group consisting of a monovalent hydrocarbon radicalcontaining more than 4 carbon atoms and oxy derivatives thereof.

2. A glyceride oil composition of improved cold test comprising aglyceride oil having incorporated therein a small amount of anoil-soluble product to improve the cold test thereof, said product beinga polymerization product of a substituted vinyl compound according tothe general formula wherein X is an alkyl radical and R is an allphaticmonohydric saturated alcohol radical having more than 12 carbon atoms.

3. A glyceride oil composition of improved cold test comprising aglyceride oil containing relatively high melting point constituentshaving in-v corporated therein a small amount of an oilsoluble productto improve the cold test thereof, said product being the polymerizationproduct of an ester of acrylic acid and a monohydric saturated alcoholcontaining more than 12 carbon atoms per molecule.

4. A glyceride oil composition of improved cold test comprising aglyceride oil containing relatively high melting point constituentshaving incorporated therein a small amount of an oilsoluble product toimprove the cold test thereof, said product being the polymerizationproduct of an alpha-alkyl substituted acrylic acid and a monohydricsaturated alcohol containing more than 12 carbon atoms per molecule.

5. A glyceride oil composition of improved cold test comprising aglyceride oil containing relatively high melting point constituentshaving incorporated therein a small amount of an oil-solublepolymerization product in an amount between .005 and 1.0 per cent byweight to improve the cold test thereof, said product being a member ofa group consisting of lauryl, cetyl, and octadecyl esters ofalpha-methacrylic acid.

6. In a method of separating a glyceride fatty material into higher andlower melting point constituents by fractionating the liquefied fattymaterial, the improvement which comprises dispersing throughout the saidfatty material a small amountof an oil soluble crystal modifying productto increase the rate at which the relatively high melting point crystalssettle, said product being the polymerization product of esterscontaining a radical selected from the group consisting of vinyl andsubstituted vinyl radicals according to the general formula wherein X isselected from the group consisting of hydrogen and alkyl and aromatichydrocarbon radicals and Y is selected from the group having the formulat oo-R and wherein R. is selected from the group consisting of amonovalent hydrocarbon radical containing more than 4 carbon atoms andoxy derivatives thereof.

7. An improved method of separating a glyceride fatty material intohigher and lower melting point constituents, which comprises dispersingthroughout a liquefied glyceride fatty material a small amount of anoil-soluble polymerization product of esters containing a radicalselected from the group consisting of vinyl and substituted vinylradicals according to the general formula wherein X is selected from thegroup consisting of hydrogen and alkyl and aromatic hydrocarbon radicalsand Y is selected from the group having the formula and wherein R isselected from the group consisting of a monovalent hydrocarbon radicalcontaining more than 4 carbon atoms and oxy derivatives thereof, coolingthe said fatty material containing the added polymerization product tocrystalide fatty material into higher and lower melting pointconstituents, which comprises dispersing throughout a liquefiedglyceride fatty material a small amount of an oil-soluble polymerization7 product of a substituted vinyl compound. having the general formula XCH2=-% JO-R wherein X is an alkyl radical and R is an aliphaticmonohydric saturated alcohol radical having more than 12 carbon atoms,cooling the said fatty material containing the added polymerizationproduct to crystallize the higher melting point constituents, andseparating the said constituents from the lower melting pointconstituents remaining in the liquid glyceride fatty material, thecrystals of said higher melting point constituents formed on coolingbeing similar and better dofined to facilitate separation from the saidlower melting point constituents.

9. An improved method of separating a glyceride fatty materialinto'higher and lower melting point constituents, which comprisesdispersing throughout a liquefied glyceride fatty material a "smallamount of an oil-soluble polymerization product of an ester of acrylicacid and monohydric saturated alcohol containing more than 12 carbonatoms per molecule, cooling the said fatty material containing the addedpolymerization product to crystallize the higher melting pointconstituents, and separating the said constituents from the lowermelting point constituents remaining in the liquid glyceride fattymaterial, the crystals of said higher melting point constituents formedon cooling being similar and better defined to facilitate separationfrom the said lower melting point constituents.

10. An improved method of separating a glyceride fatty material intohigher and lower melting point constituents, which comprises dispersingthroughout a liquefied glyceride fatty material a small amount of anoil-soluble polymerization product of an alpha-alkyl aryl substitutedacrylic acid and monohydric saturated alcohol containing more than 12carbon atoms per molecule, cooling the said fatty material containingthe added polymerization product to crystallize the higher melting pointconstituents, and separating the said constituents from the lowermelting point constituents remaining in the liquid glyceride fattymaterial, the crystals of said higher melting point constituents formedon cooling being similar and better defined to facilitate separationfrom the said lower melting point constituents.

11. An improved method of separating a glyceride fatty material intohigher and lower melting point constituents, which comprises dispersingthroughout a liquefied glyceride fatty material a small amount of anoil-soluble polymerization product selected from the group consisting ofpolymerized lauryl esters of alpha-methacrylic acid, cetyl esters ofalpha-methacrylic acid, and octadecyl esters of alpha-methacrylic acid,cooling the said fatty material containing the added polymerizationproduct tocrystallize the higher melting point constituents, andseparating the said constituents from the lower melting pointconstituents remaining in the liquid glyceride fatty material, thecrystals of said higher melting point constituents formed on coolingbeing similar and better defined to facilitate separation from the saidlower melting point constituents.

' "KARL F. MATTIL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,079,336 Ralston et a1 May 4,1937 2,266,591 Eckey Dec. 16, 1941 2,418,668 Royce Apr. 8, 19472,518,917 Mattil l Aug. 15, 1950

1. A GLYCERIDE OIL COMPOSITION OF IMPROVED COLD TEST COMPRISING AGLYCERIDE OIL HAVING INCORPORATED THEREIN A SMALL AMOUNT OF ANOIL-SOLUBLE PRODUCT TO IMPROVE THE COLD TEST THEREOF, SAID PRODUCT BEINGTHE POLYMERIZATION PRODUCT OF ESTERS CONTAINING A RADICAL SELECTED FROMTHE GROUP CONSISTING OF VINYL AND SUBSTITUTED VINYL COMPOUNDS ACCORDINGTO THE GENERAL FORMULA